We report a simple and effective wet chemical technique for facile synthesis of large-scale and arrayed copper-zinc oxide nanostructures in regard to high performance of hydrogen production. The zinc oxide arrays as support were grown by a template-free aqueous route and subsequently the copper catalysts were impregnated on zinc oxide surface at low temperature by means of spontaneous reduction to form the hierarchical core-shell type nanostructures. Systematic analyses were employed to examine morphological, component, and structural characterizations of arrayed copper-zinc oxide nanostructures. In particular, these nanocomposites exhibited high methanol conversion, hydrogen production, and carbon dioxide selectivity at lower reaction temperature in comparison with the conventional catalysts. As shown above, our work here could open up new possibilities for the preparation of core-shell type copper-zinc oxide nanocomposites in micro reformed hydrogen fuel cell (RHFC) devices applications.